Cyclic unsaturated compounds have been known as a skeleton which shows physiological activity, and have been expected to be used as a monomer for producing polymers having characteristics such as heat resistance, optical property, UV curability, and adherence, as well as an intermediate for pharmaceuticals and agrichemicals such as an antitumor agent and an antivirotic. Polymers obtained from such monomers can be used as raw materials for various chemical products such as an electronic and informational material, an optical material, a photosensitive material, a coating material, an adhesive, a detergent builder, or raw materials for pharmaceuticals and agrichemicals. Thus, the cyclic unsaturated compounds are useful in chemical, pharmaceutical, and agrichemical fields.
As a conventional production method of such a cyclic unsaturated compound, a method for producing α-methylene-γ(gamma)-butyrolactones using cyclic reaction of 4-hydroxy-2-methylenebutanoic acid and cyclic reaction of 2-methylene-4-pentanoic acid was disclosed (for example, refer to Hoffmann, H. M. R.), and 1 other, “Angewandte Chemie International Edition in English”, (Germany), VCH, 1985, vol. 24, No. 2, p. 94 to 110). Further, a method for producing α-methylene-γ-butyrolactone from γ-butyrolactone and formaldehyde using a basic compound was disclosed (for example, refer to U.S. Pat. No. 6,232,474 and Japanese Kokai Publication No. Hei-10-120672). However, these methods have room for improvement in order to be applied to industrial production because expensive organic reagents are used; reactions are performed in multiple stages; reaction conditions such as temperature are severe in the reaction steps; deterioration of the catalyst is easily caused; and such methods are inferior in terms of cost.
A method for producing α-methylene-γ-butyrolactones from a triple bond-containing alcohol and carbon monoxide using palladium as a catalyst was disclosed (for example, refer to Murray, T. F., and three others “Journal of the American Chemical Society” (U.S.) American Chemical Society, 1981, vol. 103, p. 7520 to 7528). However, such a method has room for improvement in order to be applied to industrial production because expensive raw materials and carbon monoxide with high toxicity are used and therefore such a method is inferior in terms of cost and safety.
Further, a method for producing α-methylene-γ-butyrolactones from an unsaturated alcohol in which halogen is bonded to a double bond and carbon monoxide using nickel was disclosed (for example, refer to Semmelhack, M. F., and one other, “Journal of the American Chemical Society”, (U.S.) American Chemical Society, 1981, vol. 103, p. 3945 to 3947). However, such a method has room for improvement in order to be applied to industrial production because expensive raw materials and carbon monoxide with high toxicity are used and therefore such a method is inferior in cost and safety.
With respect to reactions utilizing acryloxy palladation or methacryloxy palladation of alkene, methods for producing unsaturated chain esters typified by acrylic esters and methacrylic esters or unsaturated cyclic esters typified by α-methylene-γ-butyrolactones using palladium acetate/benzoquinone/manganese dioxide catalytic system were disclosed (for example, refer to Ferret, N., and three others, “Journal of Chemical Society Chemical Communication”, (Britain), Royal Society of Chemistry, 1994, No. 22, p. 2589 to 2590). Table 1 in the document of Ferret et al. discloses a reaction utilizing typical acryloxy palladation of alkene by acrylic acid or methacrylic acid using this catalytic system. For example, Example 7 shows a reaction using acrylic acid and norbornene. However, the reaction rate is insufficient and therefore the productivity is low. Further, it is found that if a reaction is performed by this known art using acrylic acid and ethylene as starting materials, vinyl acrylate is overwhelmingly generated more than α-methylene-γ-butyrolactone and therefore the selectivity of the desired α-methylene-γ-butyrolactone is extremely low. Therefore, such a reaction has room for improvement in order to be a method for producing cyclic unsaturated compounds, which has high versatility not depending on the kind of substrates and high productivity.
With respect to reactions using intramolecular acryloxy palladation of alkene, a method for producing unsaturated cyclic esters typified by α-methylene-γ-butyrolactones using palladium acetate/benzoquinone/manganese dioxide catalytic system or palladium acetate/sodium acetate/oxygen catalytic system was disclosed (for example, refer to Jabre-Truffert, S., and one other, “Tetrahedron Letters”, (Britain), Elsevier Science, 1997, vol. 38, p. 835 to 836). However, it is found that if a reaction is performed under conditions of this known art using acrylic acid and ethylene as starting materials, vinyl acrylate is overwhelmingly generated more than α-methylene-γ-butyrolactone and the reaction hardly proceeds. In addition, there was not disclosure about the intermolecular reaction and starting materials produced through multiple steps must be used for the intramolecular cyclic reaction and therefore such a method is inferior in cost. Therefore, such a method has room for improvement in order to be applied to industrial production.
Further, a solid catalyst containing palladium and tellurium, its production method, and a method for producing an oxidation reaction product by performing diacetoxylation of butadiene using the catalyst was disclosed (for example, refer to Japanese Kokoku Publication No. Sho-52-29726, Japanese Kokoku Publication No. Sho-52-29727, Japanese Kokoku Publication No. Sho-52-12685, Japanese Kokoku Publication No. Sho-52-12171, Japanese Kokai Publication No. Sho-51-63119, Japanese Kokai Publication No. 2005-34720, Japanese Kokai Publication No. 2005-13800, Japanese Kokai Publication No. 2005-105336, Takehira, K., and two others, “Journal of Catalysis” (U.S.), Elsevier Science, 1979, vol. 58, p. 155 to 169). For example, butadiene is coordinated to palladium, and one acetic acid (acetate) attacks an end of a double bond and is bonded thereto, followed by formation of a π(pi)-allyl palladium species, and successively, another acetic acid (acetate) attacks an end of the π-allyl site, thereby generating 1,4-diacetoxy-2-butene. However, such methods are not preferably applied to methods for producing cyclic unsaturated compounds because of the reaction mechanisms and the like. Therefore, methods for producing cyclic unsaturated compounds, which permit excellent yield and reaction rate have been desired.
Further, a method for producing lactone compounds containing a vinyl group at the α position from a β,γ-unsaturated carboxylic acid and an epoxy compound was disclosed (for example, refer to Fujita, T., and four others, Chemistry & Industry, (Britain), 1983, p. 897). Further, a method for producing lactone compounds containing a vinyl group at the α position from 4-vinyl-1,3-dioxane-2-one using palladium as a catalyst was disclosed (for example, refer to Bando, T., and four others, “Bulletin of the Chemical Society of Japan”, (Japan), the Chemical Society of Japan, 1992, vol. 65, p. 97 to 110). However, these methods have room for improvement in order to be applied to industrial production because expensive organic reagents such as lithium naphthalenide are needed and expensive starting material substrates and carbon monoxide with high toxicity must be used and therefore such methods are inferior in cost and safety.